Compound catalyst



atented Apr. 30, 1935 UNITED STATES PATENT OFFICE COMPOUND CATALYST Donald R. Stevens, Pittsburgh, and William A. Gruse, Wilkinsburg, Pa., assignors to Gulf Refining Company, Pittsburgh, Pa., a corporation of Texas No Drawing. Application November 3, 1931, Serial No. 572,882

3 Claims. (01. 23-233) This invention relates to compound catalysts; Where compositions are wanted with an energy and it comprises a catalyst useful in relations of reaction intermediate between that of pure where the catalytic activity of anhydrous alumialuminum chlorid and that of the equimolecular num chlorid is desired in a milder form, such combination of a phenol and aluminum chlorid,

5 catalyst consisting of a compound of aluminum the proportion of phenol in the composition is 5 chlorid with a phenol, such as phenol itself, a diminished. cresol, or a naphthol, the phenol being usually In making a composition under the present inpresent in equimolecular proportions or-less; all vention, aluminum chlorid is pulped mechanically as more fully hereinafter set forth and as claimed. with the required proportion of a phenol without As is well known, aluminum chlorid is a useful heating, during which procedure substantially no 10 catalyst in various processes of purifying pe- IICl is evolved. Commercial cresylic acid, which troleum oils by obviating or reducing unsaturai's a mixture of the cresols, makes a good catalyst. tion, by removing sulfur compounds, etc., and is oiwever, we often use phenol itself, which is also useful as a depolymerizing catalyst adapted "omewhat more expensive. For special purposes,

to form low'boiling oils, like gasoline, at the exit gives a particularly advantageous catalyst. 15 pense of higher boiling oils, such as gas oil. These Phenol-aluminum chlorid catalysts give low polytwo functions of aluminum chlorid are quite dismerization losses; but cresylic acids give comtinct, but it is diificult in most cases to obtain plexes of more general utility. the purifying action, as distinguished from the A catalyst under the present invention, made depolymerizing action, alone. Ordinarily, reby combining equi-molecular proportions of alu- 20 course is to low temperature operation when the ninum chlorid and of commercial cresylic acid, refining action alone is wanted. For example, in s a heavy, dark brown or red liquid. It is useful treating lubricating oil and paraflin, where no in refining oil and in making gasoline in exactly formation of low boiling oils is wanted, it is the the same manner as aluminum chlorid. For con- Practice to limit the temperature to say, 150 F. version it is used in the same amount, making 25 At these low temperatures, these materials are allowance for the phenol present. For refining, quite viscous and mechanical difliculties are enless may be used. It is not necessary, as is the countered in keeping the aluminum chlorid in case with aluminum chlorid alone, to pulp the suspension in the oil to be refined. It is desircatalyst with oil prior to adding it to the oil to be able to be able to operate at somewhat higher treated since the catalyst is itself liquid. Howtemperature ranges without obtaining production ever, it is sometimes convenient to dilute the of gasoline and low boiling oils. And in the procatalyst with some of the oil with which it is subduction of gasoline and low boiling oils at a higher sequently to be used. Thinning may be done with range of temperatures, the action of the alumicommercial benzol or aromatic-rich petroleum num chlorid is occasionally too violent. naphthas. Excess cresols may also be used for 35 We have found that by combining aluminum thinning purposes. 4 chlorid with a phenol in equimolecular propor- In refining, the present catalyst does not extions, a thick liquid composition is obtained which hibit some of the undesirable reactions of alumiis readily stirred into oils. This composition has num chlorid used alone. For instance, polymeriabout the same totalamount of activity per zation is reduced. The use of the present cata 40 pound of aluminum chlorid contained, but its lystleadstono loss of anti-knock value. action is slower and milder. With the compound In using the present catalyst for conversion catalyst of the present invention,.it is permissible reactions, that. is in the production of lower boilin refining lubricating oil and paraflin to heat ing oils, the formation of cake, which is an unto higher temperatures than usual, thereby reprofitable incident of the use of ordinary alumi- 45 ducing the viscosity of the mixture, without the num chlorid, is reduced. There is also less forrisk of forming low boiling oils. In other words, mation of gas.- There is some indication that none of the lubricating oil is converted into less there is a greater production of cyclic compounds valuable, less viscous material; in the use of the present catalyst than is the case Aluminum chlorid, as it is found in commerce, with aluminum chlorid alone. often contains several per cent of ferric chlorid; In making the present compound catalyst, imthis originating in the bauxite used as a raw mapure commercial phenols, such as cresylio acid, terial. For the present purposes, aluminum containing neutral hydrocarbons can be used. chlorid containing ferric chlorid is equivalent to As illustrating the difference in properties of 56 pure aluminum chlorid. the present catalysts as compared with aluminum chlorid may be cited some work in which a solar oil treated with 2 per cent of anhydrous aluminum chlorid at 450 C. gave a gasoline yield of 47 per cent, a coke loss of 4.4 per cent and a gas loss of 18 per cent. On the other hand using one of the present catalysts, a complex of aluminum chlorid with an equal molecular proportion of ordinary phenol, a 2 per cent addition (calculated on the aluminum chlorid) gave a gasoline yield of 44 per cent with zero coke loss and a gasloss of 15 per cent. The temperature of conversion was the same. The complex catalyst gave a little less gasoline but the loss and deterioration of residual oil were considerably less. This was in a converting operation. Making a similar comparison of a refining operation, a cracked gasoline distillate treated at C. with 1 per cent of aluminum chlorid gave good results as far as refining went. The loss by polymerization was 9.5 per cent. On repeating the treatment with the same gasoline and with the same amount of aluminum chlorid, combined however with phenol in equal molecular proportions, there was obtained the same degree of refining with a polymerization loss of but 1.5. With aluminum chlorid alone, the loss of oil to sludge was 2.5 per cent while with a compound catalyst the similar.

loss as sludge was only 0.5 per cent. In a general way, it is found that 0.6 per cent of aluminum chlorid combined with phenol is about as effective as 1 per cent of aluminum chlorid used alone.

The compound catalyst of the present invention is not only useful in converting and refining operations of the ordinary type but it is also adapted, under suitable conditions, for converting gaseous hydrocarbons into liquid; or for inducing condensation of gaseous hydrocarbons with liquid hydrocarbons; as in causing relative- Certain processes wherein the catalyst of our I present invention is employed for the improvement of petroleum products are described and claimed in our copending application Serial No. 578,412, filed December 1, 1931.

What we claim is:

1. As a catalyst for reactions involving petroleum oils and the like, a composition of matter consisting of aluminum chloride and a phenol in which the anhydrous aluminum chloride and the phenol are present in substantially equimolecular proportions.

2. As a catalyst for reactions involving petroleum oils and the like, a composition consisting of aluminum chloride and aphenol; the aluminum chloride being present in a proportion not less than equimolecular.

3. As a catalyst Ior reactions involving petroleum oils and the like, a composition of matter consisting of anhydous aluminum chloride and commercial cresylic acid; the amount of cresylic acid in the composition being not substantially greater than that corresponding to equimolecular proportions.

DONALD R. STEVENS. VVJLLIAM A. GRUSE. 

